狄氏剂、艾氏剂、氯丹、七氯化茚、氯啶初步总结报告——环戊二烯系农药研究(Ⅰ)

一、绪言农药狄氏剂、艾氏剂、及氯化茚等有高效杀虫力,已为世界各国所熟知,并已广泛采用。其主要原料为环戊二烯,而在制造过程中,必先制得中间体六氯环戊二烯;然后,以六氯环戊二烯为主体,制得许多衍生物,包括狄氏剂、艾氏剂及氯化茚等农药。此类化合物,在化学上属于狄艾二氏反应(Diels-Aldr reaction)结果所得一系列的缩合物。根据国外文献报导,中间体六氯环戊二烯,不但可制成农业杀虫剂,艾可制成杀菌剂、植物生长剂、润滑油及耐高压加入剂等。因此,六氯环戊二烯的合成,是一系列衍生物的主要关键性中间     

全氯戊环癸烷的研制

利用可分离出环戊二烯的C_5馏分与Cl_2反应,得到六氯环戊二烯,六氯环戊二烯在无水AlCl_3催化下发生二聚反应,产物在室温下加水洗去Al~(3+),然后干燥得到雪白的全氯戊环癸烷结晶。     

《安邦报》报消息 市场是心 信誉是途 六氯环戊二烯生产再创历史新高

六氯环戊二烯车间继七月份创下历史最高产170吨的记录，八月份又谱写历史新纪元，本月累计生产176．16吨。     

由C5馏分合成六氯环戊二烯

本文研究以C_5馏分和氯气为原料通过气相连续氯化合成六氯环戊二烯的方法,对反应的影响因素进行了讨论。     

国内外简讯

无水氯化镁制备技术；安邦六氯环戊二烯项目通过验收；单氯代苯酐投产；山东曙光氯化聚乙烯扩产；硫氰酸钠制异形腈纶……     

得克隆的合成及在尼龙66中的应用

用二甲苯作溶剂,六氯环戊二烯与环辛二烯量比2.1∶1,反应温度160~170℃,反应时间4 h,合成得克隆,收率达到95.0%。     

三氯乙烯生产新工艺

介绍以乙炔、氯气为原料生产四氯乙烷,四氯乙烷再与乙炔催化重整生成三氯乙烯联产氯乙烯的工艺方法,并通过试验得到三氯乙烯收率较高的工艺条件：四氯乙烷流量为2．8 mL/min,四氯乙烷与乙炔的摩尔比为1∶1,温度为200℃,压力为0．1 MPa。     

硫丹合成工艺的研究

研究了硫丹的非溶剂合成路线，以六氯环戊二烯为原料，采用的合成方法工艺简单，产品收率以HCCP计为75.6%，原药有效成分含量≥94%。     

10%四氯虫酰胺悬浮剂对甜菜夜蛾的室内毒力测定及田间药效评价

为明确10%四氯虫酰胺悬浮剂对甜菜夜蛾的防治效果,开展了室内毒力测定和田间药效评价。结果表明:四氯虫酰胺对甜菜夜蛾具有较好的防治效果,95%四氯虫酰胺原药对甜菜夜蛾的LC50值为0.123 7 mg/L。10%四氯虫酰胺悬浮剂有效成分用量为30～60 g/hm~2时,药后3 d、7 d、10 d对甜菜夜蛾的田间防治效果大于90%。     

四氯邻苯二甲酸酐的高效液相色谱分析方法研究

四氯邻苯二甲酸酐是白色结晶或无色棱形针状晶体,主要用于医药、农药、染料、颜料等中间体、树脂阻燃剂、塑料增强剂。四氯邻苯二甲酸酐的分析方法一是以乙酸铵和甲醇为流动相的高效液相色谱方法,二是用甲醇将四氯邻苯二甲酸酐进行酯化,用乙腈加三氟乙酸水溶液作流动相的高效液相色谱方法。本文研究的方法是四氯邻苯二甲酸酐与氢氧化钠溶液反应生成钠盐,以甲醇和磷酸水溶液为流动相的高效液相色谱方法。     

3,3-二甲基-1-丁烯合成条件的优化

探讨了合成3,3-二甲基-1-丁烯（新己烯）的最佳工艺条件。以叔丁醇和盐酸为原料,浓硫酸为催化剂合成氯代叔丁烷,探讨了反应温度和反应时间对收率的影响;采用加压方法,无水AlCl3为催化剂,以氯代叔丁烷和乙烯为原料合成氯代新己烷（2,2-二甲基丁烷）;确定了合适的加成反应条件,以N-甲基吡咯烷酮为溶剂,采用反应精馏的方法,氯代新己烷脱氯化氢制备新己烯。实验确定的最佳工艺条件：合成氯代叔丁烷的最佳反应温度为20℃,最佳反应时间为60 min;合成氯代新己烷的最佳反应压力为0.75 MPa,最佳反应温度为45℃;脱氯化氢制备新己烯的最佳溶剂为N-甲基吡咯烷酮。     

Electron-beam lithography of chlorinated polystyrenes with narrow molecular weight distributions

Polystyrenes with narrow molecular weight distributions have been chlorinated with only slight broadening of molecular weight distributions to yield materials that are five to six times more sensitive to electron-beam irradiation. The chlorinated polystyrenes are useful negative resists for electron-beam lithography. At molecular weights of 3-4 × 10⁵g/mole, their threshold sensitivities to 20 keV electrons are 1-2μC/cm². Their lithographic contrasts are ≥ 1.5; in fact, > 2.0 for the narrowest molecular weight distributions. They compare favorably in these regards to polystyrenes of similar molecular weight characteristics. Lithographic relief images that are 80% of the original thickness of the polymer film can be formed at three to four times the threshold dose. The degree of chlorination ranged from 0.65-0.76 Cl/monomer unit. The infrared spectra of the chlorinated materials resemble the spectrum for poly(4-chlorostyrene). Elemental analysis indicated, however that some addition of chlorine had occurred. More extensive chlorination or chlorination of the higher molecular weight starting materials broadened the molecular weight distributions. The chlorinated material, a kind of poly(4-chlorostyrene-costyrene), is less sensitive than poly(4-chlorostyrenc) prepared by addition polymerization by almost a factor of four.     

不同维度纳米填料改性氯化聚乙烯橡胶的研究进展

综述纳米二氧化硅、碳纳米管、石墨烯等多种不同维度纳米填料改性氯化聚乙烯橡胶的研究进展。介绍利用不同填料改性氯化聚乙烯橡胶的机理及改性后氯化聚乙烯橡胶的应用概况,提出不同填料改性氯化聚乙烯橡胶的性能优化和应用的展望。     

Applications de la spectrométrie de rayons x à l'analyse de matériaux macromoléculaires. II. Etude de polyéthylènes chlorés en surface

The chlorine concentrations in the range up to about 500 μg.cm^-2 of surface chlorinated polyethylene films were determined by X-ray fluorescence spectrometry. By using appropriate standards, it is shown that the investigated samples can be regarded as thin films only when the energy of the «equivalent» primary X-radiation is high enough. Results allow to estimate (in the range up to about 4 μm) the chlorinated film thicknesses versus duration of the halogenation processes.     

HPLC-UV同时测定皮革中三种含氯苯酚

建立并验证了用HPLC-UV测定皮革中含氯苯酚的方法;以丙酮为溶剂,采用超声波提取法提取皮革中含氯苯酚,以相对保留时间定性,峰面积进行定量;该方法平均回收率为97.20%~103.11%,RSD为1.094%~1.377%,检测限(S/N=3)分别为2,3,5,6-四氯苯酚:0.014 mg/L,五氯苯酚:0.002 mg/L,2,4,6-三氯苯酚:0.004 mg/L;本方法具有方便快捷、灵敏度高、回收率高、精密度好的特点,且避免了大量化学试剂的使用,减少了环境污染。     

Head-to-head polymers: 19. Chlorination of cis-1,4-polybutadiene

Chlorination of cis-1,4-polybutadiene (PB) has been studied in detail. It was found that chlorination must be carried out in an oxygen free atmosphere at polymer concentrations below 0.5%, and at temperatures below room temperature in mixed solvents with dichloromethane as the major component. In the initial stage of chlorine addition to the double bonds of cis-1,4-polybutadiene, block structures of chlorinated segments are formed. The chlorine addition to the cis-butadiene units was not stereospecific and the final chlorination product had nearly a 1:1 ratio of the threo- and erythro structure of the CHCICHCI-units. Microphase separation in partially chlorinated PB was observed by d.s.c., dynamic-mechanical measurement, and transmission electron microscopy. It was concluded that partially chlorinated PB, whose degree of chlorination was lower than 65 mole %, was composed of almost pure cis-1,4-PB domains and a separate phase which consists ofCH₂CHCICHCICH₂units with perhaps as much as 10% of cis-1,4-PB units incorporated in this phase. If the degree of chlorination is more than 90 mole % one phase exists.     

Influence of chlorinated paraffin on properties of silica filled polychloroprene

Abstract

Roles of the two widely used chlorinated paraffins, namely Cereclor S45 and Cereclor 48, in properties of silica filled polychloroprene were investigated. The results reveal that chlorinated paraffin significantly improves the processability. The improvement is more pronounced for Cereclor S45 due to its lower viscosity. However, the addition of chlorinated paraffin has a negative effect on cure. Owing to the reduction of crosslink density and the plasticising effect of chlorinated paraffin, several mechanical properties are impaired, e.g. tensile strength, modulus, hardness, abrasion resistance as well as rebound resilience. However, the deterioration of both tensile strength and modulus is not pronounced at low loading of chlorinated paraffin (≤8·0 parts per hundred of rubber, phr). Although chlorinated paraffin has little influence on the relative tensile strength, the relative 100% modulus is affected to a greater extent due to the combination of post curing retardation and evaporation of chlorinated paraffin during thermal aging.     

Infrared spectra of chlorinated petroleum fractions

The infrared spectra of several chlorinated petroleum fractions are reported. Although the spectra of chlorinated branched and linear fractions are different in the 600–800 cm^?1 region, it is very difficult to detect less than 15% of the toxic chlorinated kerosene in mixtures with chlorinated n-paraffin waxes.     

氯碱下游产品建设投资分析(续1)

介绍了20种氯碱下游产品——氯甲苯、氯乙酸、环氧氯丙烷、氯化苄、环氧丙烷、聚偏氯乙烯树脂、氯化聚氯乙烯树脂、氯化聚乙烯、甲基氯硅烷、三氯氢硅、氯化法钛白粉、三氯化磷、4,4‘-二苯基甲烷二异氰酸酯、1,4-丁二醇、苯胺、环己酮、气相法白炭黑、甲基异丁基酮、对氨基苯酚、水合肼的市场前景、技术来源与建设投资。     

氯碱下游产品建设投资分析（续完）

介绍了20种氯碱下游产品——氯甲苯、氯乙酸、环氧氯丙烷、氯化苄、环氧丙烷、聚偏氯乙烯树脂、氯化聚氯乙烯树脂、氯化聚乙烯、甲基氯硅烷、三氯氢硅、氯化法钛白粉、三氯化磷、4,4’-二苯基甲烷二异氰酸酯、1,4-丁二醇、苯胺、环己酮、气相法白炭黑、甲基异丁基酮、对氨基苯酚、水合肼的市场前景、技术来源与建设投资。